JPH05170901A - Production of photosensitive resin - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin having excellent adhesivity and high sensitivity, comprising a high-molecular weight polyamide containing an ester bond of (meth) acrylic group by reacting the whole acid component with a diamine component and a carbodiimide in multiple stage. CONSTITUTION:In reacting (A) 100mol% dicarboxylic acid component obtained by previously reacting a tetracarboxylic acid dianhydride with a (meth) acrylic group-containing alcohol compound of formula I (R1 is bi- to hexafunctional organic group; R2 is H or CH3; (p) is l-5 integer) with (B) a diamine component composed of B1: 0.5-5wt.% diaminosiloxane of formula II (R3 and R4 are bifunctional 1-5C aliphatic group or >=6C aromatic group; R5 and R6 are monofunctional aliphatic group or aromatic group; (n) is 1-100 integer) and B2: 99.5-50wt.% aromatic diamine by using (C) a carbodiimide as a binder, each given amount of the components B and C is added to the whole amount of the component A in multiple stage and addition of the component B1 is completed by a stage before the final stage to give the objective photosensitive resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photosensitive resin which has extremely high sensitivity, high adhesion and excellent cured film characteristics.

[0002]

2. Description of the Related Art Conventionally, a polyimide having excellent heat resistance and excellent electrical insulation and mechanical strength has been used for a surface protective film and an interlayer insulating film of a semiconductor element. Recently, a technique for imparting photosensitivity to the polyimide itself has been attracting attention in order to simplify the complicated process. For example, the following formula

[0003]

[Chemical 3]

A polyimide precursor composition having a photosensitive group with an ester group having a structure shown by
55-41422) and the like are known. All of these are dissolved in a suitable organic solvent, applied in a varnish state, dried, irradiated with ultraviolet rays through a photomask, developed, rinsed to obtain a desired pattern, and further heated to form a polyimide. It is a film. The use of photosensitized polyimide not only has the effect of simplifying the pattern creation process, but it is safe and excellent in pollution because it does not require the use of highly toxic etching solutions. It is expected that it will become an even more important technology in the future.

As a method of introducing an ester group, first, an acid dianhydride and an alcohol-containing photosensitive group are reacted with each other, and then a chlorine-containing compound such as an acid chloride is used as a condensing agent to copolymerize with a diamine (Japanese Patent Publication No. 55- No. 41422) has been reported. As a method not using a chlorine-containing compound, a method using a carbodiimide as a condensing agent (Japanese Patent Laid-Open No. 60-228537)
No. publication) is known. Resins synthesized using these carbodiimides have the advantage of having a low chlorine content of several ppm or less, but have the following problems.

[0006] Generally, carbodiimides are condensing agents used when synthesizing peptides from amino acids. For example,
N, N'-dicyclohexylcarbodiimide (hereinafter abbreviated as DCC) is highly reactive with carboxylic acid, firstly O-acylisourea is produced, and then further reacted with another molecule of carboxyl component to become a symmetrical acid anhydride, This anhydride reacts with an amine to form an amide bond. However, in this reaction, if a strongly basic amine is present in the reaction system, as a side reaction, O-acylisourea is rearranged to produce an inactive acylurea as a byproduct.

When a photosensitive resin is obtained, a polyamide is obtained from a dicarboxylic acid having an acryl or methacryl group obtained by reacting an alcohol compound represented by the formula (1) with an acid dianhydride, and a carbodiimide from a diamine. In this case, the above-mentioned by-product, acylurea, is formed, and the terminal ends, which makes it extremely difficult to increase the molecular weight. Therefore, there is also a method of carrying out the reaction at a low temperature in order to suppress this, but it is difficult to completely suppress it due to heat generation due to the reaction, and only a low molecular weight polyamide can be obtained.
In addition, various studies have also been conducted on the reaction method, for example,
The Chemical Society of Japan, Vol. 80, No. 12, p. 1497, acid, amine and DC
Instead of adding all the amount of C from the beginning to react,
It is reported that the by-product of N-acylurea can be suppressed by reacting CC for a while and then gradually dropping the amine.

However, the fact is that even if polyamide is synthesized by this method, only low molecular weight polyamide can be obtained. Further, when a part of the diaminosiloxane represented by the formula (2) is used as the diamine component, there is a drawback that the molecular weight becomes smaller. The reason for this is considered that the reactivity of diaminosiloxane is generally inferior to that of aromatic diamine. Only a very brittle film can be obtained from a photosensitive resin composition using such a low molecular weight polyamide. Further, in the case of a photosensitive resin, if the molecular weight of the base resin is low, there is a drawback that the sensitivity is lowered.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a photosensitive resin which has excellent adhesion and high sensitivity.

[0010]

Means for Solving the Problems The present invention comprises 100 mol% of a dicarboxylic acid component obtained by previously reacting a tetracarboxylic dianhydride and an alcohol compound having an acrylic group or a methacrylic group represented by the formula (1), 0.5 to 50 mol% of diaminosiloxane represented by the formula (2) and aromatic diamine 99.
When reacting a diamine component consisting of 5 to 50 mol% with carbodiimides as a condensing agent, for all acid components, the required diamine components and carbodiimides are added and reacted in predetermined stages in multiple stages, and The method for producing a photosensitive resin is characterized in that the addition of diaminosiloxane is completed before the final stage of addition.

[0011]

[Chemical 1]

[0012]

[Chemical 2]

[0013]

The carbodiimides in the present invention are generally condensing agents used when synthesizing peptides from amino acids. In the present invention, the carbodiimides are used as a condensing agent when obtaining a polyamide from a dicarboxylic acid and a diamine, and the reaction mechanism is as follows.

First, when an equimolar amount of carbodiimides is added to dicarboxylic acid, dicarboxylic acid and carbodiimides form a condensation intermediate and then react with the remaining carboxyl group, that is, from two molecules of dicarboxylic acid to acid anhydride. The reaction proceeds in the form of forming a substance, and then 1/2 mol of diamine is added to the dicarboxylic acid to react. As a result, 1/2 mol of the dicarboxylic acid forms an amide bond, and the remaining 1/2 mol returns to the carboxyl group. Then, the carboxylic acid is added again to equimolar amounts of the dicarboxylic acid to proceed the reaction to form an acid anhydride.
Add / 4 mol of diamine and react. After that, while repeating the same reaction, the increase in the molecular weight proceeds.

Here, the conventional method, that is,
When dicarboxylic acid is dissolved in a solvent, carbodiimides are added in an amount of 2 times the molar amount of the dicarboxylic acid, and then diamine is added in an equimolar amount to the dicarboxylic acid. Equivalent amounts of diamine will be present and half of the diamine will remain unreacted and free. Due to its basicity, O-acyl isourea is rearranged, and unreactive acyl urea is easily generated. As a result, the subsequent reaction of increasing the molecular weight is hindered, and the molecular weight of the obtained polyimide becomes very small.

When a part of the diamine component is a diaminosiloxane represented by the formula (2), only a polyamide having a lower molecular weight can be obtained. However, as in the present invention, when carbodiimides and diamine components are synthesized in multiple stages, and when diaminosiloxane is added up to the stage prior to the final stage, the side reaction as described above is unlikely to occur, and the molecular weight of the obtained polyamide is low. Will also be very large.

Specifically, the reaction is carried out by the following method.
After dicarboxylic acid is dissolved in a solvent, carbodiimides in an equimolar amount to dicarboxylic acid are added and reacted for a while, and then ½ mol of dicarboxylic acid diamine is added and reacted for a while. Next, carbodiimides in an equimolar amount to dicarboxylic acid are added and reacted for a while in the same manner, and then diamine corresponding to ½ mol of dicarboxylic acid is added to synthesize a polyamide.

Here, in the case of the present invention in which the diamine component contains both a highly reactive diamine (for example, an aromatic diamine) and a low reactive diamine (for example, diaminosiloxane), the first reactive diamine is selected. In addition, better results can be obtained by adding a highly reactive diamine for the second time. The diamine component with low reactivity is dicarboxylic acid
If it is less than 1/2 mol, add highly reactive diamine to add 1
Make the second addition diamine to be 1/2 of the dicarboxylic acid. As the diamine added for the second time, the remaining highly reactive diamine is added. As described above, the diamine having low reactivity is first added and reacted, so that the reaction can be performed preferentially, and as a result, the molecular weight of the obtained polyamide also becomes high.

The method shown here is a method in which carbodiimides and diamines are added in ½ moles each, but in order to more completely suppress the production of acylurea, the carbodiimides and diamines added a second time 1/2 the amount
It is preferable to add them in two portions (addition in three portions). Theoretically, it is conceivable to divide into 4 divisions and 5 divisions and (1/2) ⁿ each, but practically 2 to 3 divisions are sufficient.

The carbodiimides used in the present invention include dicyclohexylcarbodiimide, ethylcyclohexylcarbodiimide, diethylcarbodiimide, diphenylcarbodiimide, diisopropylcarbodiimide and the like.

The tetracarboxylic dianhydride used in the present invention is mainly an aromatic tetracarboxylic dianhydride or a derivative thereof. For example, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3 , 3'-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride,
Naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride , Naphthalene-1,
2,6,7-Tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,
3,5,6,7-Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2 , 3,6,7-tetracarboxylic dianhydride,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6, 7-tetrachloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2',
3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4'
-Diphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-
Terphenyl tetracarboxylic dianhydride, 2,2 ", 3,3" -p-
Terphenyl tetracarboxylic dianhydride, 2,3,3 ", 4" -p-
Terphenyl tetracarboxylic dianhydride, 2,2-bis (2,3
-Dicarboxyphenyl) -propane dianhydride, 2,2-bis
(3,4-dicarboxyphenyl) -propane dianhydride, bis
(2,3-dicarboxyphenyl) ether dianhydride, bis
(3,4-dicarboxyphenyl) ether dianhydride, bis
(2,3-dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3- Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-
Tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12 -Tetracarboxylic acid dianhydride, phenanthrene-1,2,7,8-tetracarboxylic acid dianhydride, phenanthrene-1,2,6,7-tetracarboxylic acid dianhydride, phenanthrene-1,2,9, 10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3, 4,5-tetracarboxylic dianhydride,
Examples thereof include, but are not limited to, thiophene-2,3,4,5-tetracarboxylic dianhydride. Further, in use, one kind or a mixture of two or more kinds may be used. You may mix aromatic tricarboxylic acid or its derivative (s), trimellitic anhydride, etc.

The diamine used in the present invention is an aromatic diamine and / or its derivative. For example, m-phenylene-diamine, 1-isopropyl-2,4-phenylene-diamine, p-phenylene-diamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'- Diamino-diphenylethane, 3,3'-diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 4,4'-diamino-diphenylsulfide, 3,3'-diamino- Diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3 '
-Diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, benzidine, 3,3'-diamino-biphenyl, 3,3'-dimethyl-
4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine, 4,4 "-diamino-p-terphenyl, 3,3" -diamino-p-
Terphenyl, bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis
(2-methyl-4-amino-pentyl) benzene, p-bis (1,1-
Dimethyl-5-amino-pentyl) benzene, 1,5-diamino-
Naphthalene, 2,6-diamino-naphthalene, 2,4-bis (β-
Amino-t-butyl) toluene, 2,4-diamino-toluene, m
-Xylene-2,5-diamine, p-xylene-2,5-diamine, m
-Xylylene-diamine, p-xylylene-diamine, 2,6-
Diamino-pyridine, 2,5-diamino-pyridine, 2,5-diamino-1,3,4-oxadiazole, 1,4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine, 2,2-Dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene-diamine, hexamethylene-diamine, 2,5-dimethyl
-Hexamethylene-diamine, 3-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl
-Heptamethylene-diamine, 3-methyl-heptamethylene-
Diamine, 4,4-dimethyl-heptamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methyl-nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,10-diamino- 1,10-dimethyl-decane, 2,11-diamino-dodecane,
1,12-diamino-octadecane, 2,12-diamino-octadecane, 2,17-diamino-icosane, diaminosiloxane, 2,6-diamino-4-carboxylic benzene, 3,3'-
Examples thereof include, but are not limited to, diamino-4,4′-dicarboxylic benzidine. In use, one kind or a mixture of two or more kinds may be used.

The alcohol compound having an acryl or methacryl group used in the present invention is reacted with an aromatic tetracarboxylic acid or a derivative thereof and an aromatic tricarboxylic acid or a derivative thereof to form a dicarboxylic acid compound having an acryl or methacryl group. , And further condenses with a diamine to form a polyamide. Here, this alcohol compound becomes a raw material of a negative photosensitive resin by binding to a polyamide side chain by an ester bond and further subjecting these acrylic or methacrylic groups to a photocrosslinking reaction. In an alcohol compound having an acrylic or methacrylic group, the number of acrylic or methacrylic groups (Formula (1)
As for p) therein, 1 to 5 is preferable. In the case of 0, since acrylic or methacrylic acid is not contained, the photocrosslinking reaction does not proceed, which is not preferable. On the other hand, when it is 6 or more, not only is it industrially difficult to produce, but also the molecular weight becomes large and the compatibility with the polyamic acid decreases, which is not preferable. Examples of the alcohol compound having an acryl or methacryl group include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and glycerol diacrylate. , Glycerol dimethacrylate, glycerol acrylate methacrylate, trimethylolpropane diacrylate, 1,3-diacryloylethyl-5-hydroxyethyl isocyanurate, 1,3-dimethacrylate-5-hydroxyethyl isocyanurate, ethylene glycol modified pentaerythritol Triacrylate, propylene glycol modified PET Taerythritol triacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, polyethylene glycol modified Examples thereof include, but are not limited to, methacrylate, polyethylene glycol-modified acrylate, polypropylene glycol-modified acrylate, polypropylene glycol-modified methacrylate, and the like. In using these, one kind or a mixture of two or more kinds may be used.

The diaminosiloxane represented by the formula (2) used in the present invention has the effects of improving the adhesion and lowering the elastic modulus. The degree of polymerization n of the diaminosiloxane must be 1 to 50. If n is less than 1, the effect of improving the adhesiveness and lowering the elastic modulus cannot be obtained, and the length of n exceeds 50. When a chain diaminosiloxane is used, the reaction becomes difficult to proceed quantitatively even if it is added twice, and it remains as an unreacted product, the molecular weight does not increase, and the flexibility decreases and cracks occur. This is not preferable because it becomes easier. The amount of diaminosiloxane used is 0.5 to 5 of the diamine components.
0 mol% is preferable. If it is less than 0.5 mol%, the adhesion will be improved,
The effect of lowering the elastic modulus cannot be obtained, and if it exceeds 50 mol%, the heat resistance remarkably lowers, which is not preferable.

In the present invention, the aprotic polar solvent is used for dissolving or suspending the alcohol compound having an acryl or methacryl group, the carbodiimide, and the polyamic acid. Examples of the aprotic polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-
Diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethylphosphoramide, N-methyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, methylformamide, N-acetyl-2 -Pyrrolidone, diethylene glycol monomethyl ether,
Diethylene glycol dimethyl ether is used alone or in combination. In addition to these, nonsolvents such as benzene, benzonitrile, dioxane, butyrolactone, xylene, toluene, cyclohexane and the like can be used as a solvent used in combination.

The photosensitive resin obtained according to the present invention is usually added dropwise to a poor solvent such as water, methanol or ethyl alcohol for the purpose of purifying the product to precipitate the product, which is separated by filtration, dried and then again aprotic. It is used by dissolving it in a polar solvent. As the solvent used for dissolution, an amide compound containing a carbon-carbon double bond and the like can be used in addition to the aprotic polar solvent. Examples of the amide compound containing a carbon-carbon double bond include N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide,
N, N-diethylacrylamide, N-acryloylpiperidine, N-acryloylmorpholine, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N, N-dimethylaminoethylmethacrylamide, and the like,
It is not limited to these.

Further, when the photosensitive resin obtained in the present invention is used, it is desirable to add a photosensitizer for the purpose of improving the sensitivity. The sensitizer used in the present invention is particularly 330
A compound having an absorption maximum wavelength (λmax) at ˜500 nm is preferable. When λmax is 330 nm or less, light is absorbed by the polyamic acid itself and photoreaction cannot be performed, which is not preferable. Further, when it is 500 nm or more, it causes a photoreaction with visible light, it is necessary to set a work place in a shielded room, etc., and the handleability thereof is deteriorated, which is not preferable. The sensitizer of the present invention is, for example,

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

Examples thereof include, but are not limited to: In addition, one kind or a mixture of two or more kinds may be used.

To the photosensitive resin composition according to the present invention, an adhesion aid, a leveling agent and other various fillers may be added.

To use the photosensitive resin composition obtained by the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic or an aluminum substrate. The coating method is spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Next, after prebaking at a low temperature of 60 to 80 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic rays. As actinic rays, X-rays, electron rays, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

Next, the unirradiated portion is dissolved and removed with a developing solution to obtain a relief pattern. As a developing solution, N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N
-Dimethylformamide or the like can be used, and they may be mixed with methanol, isopropyl alcohol, water, an aqueous alkaline solution or the like. As the developing method, methods such as spraying, paddle, dipping, and ultrasonic wave can be used.

Next, the relief pattern formed by development is rinsed. As the rinse liquid, xylene, methanol, ethanol, isopropyl alcohol, butyl acetate, water or the like is used. Next, heat treatment is performed to form an imide ring, and a final pattern having high heat resistance is obtained.

[0037]

The present invention will be specifically described with reference to the following examples. (Example 1) Double-division addition method 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 32
2.2 g (1.0 mol) and 2-hydroxyethyl methacrylate 26
0.3 g (2.0 mol) was dissolved in γ-butyrolactone, 166.1 g (2.1 mol) of pyridine was added, and the mixture was reacted at room temperature for 10 hours.
Then, 206.3 g (1.0 mol) of DCC dissolved in 200 g of γ-butyrolactone was added to about 20 while keeping the reaction system at 10 ° C or lower.
It dripped over minutes. 10 minutes later the following formula

[0038]

[Chemical 8]

The diaminosiloxane represented by 54.5 g (0.1
Mol), followed by 80.1 of 4,4'-diaminodiphenyl ether
g (0.5 mol) was added, and the mixture was stirred for 20 minutes. 206.3 g (1.0 mol) of DCC dissolved again in 200 g of γ-butyrolactone was added dropwise over about 20 minutes. Next, after 100.1 g (0.5 mol) of 4,4′-diaminodiphenyl ether was added, the reaction was carried out at room temperature for 5 hours to obtain a slurry-like reaction product. The dicyclohexylurea was separated by filtration and then reprecipitated in ethanol, and the solid matter was filtered and dried under reduced pressure. When the molecular weight was measured by gel permeation chromatography, the number average molecular weight was
It was as high as 21,000 and the weight average molecular weight was 52000. When the reaction rate of diaminosiloxane was calculated using'H-MNR, the reaction rate (reaction rate of the charged diaminosiloxane) was 98.1%.

Further, 100 g of the obtained polymer was added to N
-Dissolved in 150 g of methyl-2-pyrrolidone, and further 1 g of methyl ether hydroquinone as a polymerization inhibitor,
5 g of Michler's ketone (λmax 365 nm) was added as a photosensitizer and dissolved at room temperature. The obtained composition was applied onto a silicon wafer with a spinner and dried at 70 ° C. for 1 hour with a dryer to obtain a film having a thickness of about 10 μm. A resolution measuring mask made by Toppan Printing Co., Ltd. on this film (Topographic test chart N
o.1), irradiate with 1000 mJ / cm ² of ultraviolet light, and then N-
When developed with a developer containing 60% by weight of methylpyrrolidone and 40% by weight of xylene, a pattern having a resolution of 18 μm was formed.

Then, the composition was coated on a silicon wafer by the same method, the entire surface was exposed, and the steps of developing and rinsing were carried out, and the composition was further heated and cured at 150, 250 and 350 ° C. for 30 minutes each. For the adhesion test, 100 pieces were cut into 1 mm square and a cellophane tape peeling test was performed. No peeling was observed at all, and it was found that the film had high adhesion.

Separately, the composition is coated on an aluminum plate,
After exposing the entire surface, developing, rinsing and heat curing, the aluminum plate was removed by etching to obtain a film. The tensile modulus of elasticity (JIS K-6760) of this film was as small as 180 kg / mm ² .

(Examples 2 to 6 and Comparative Examples 1 to 4) Conditions for the number of times DCC and diaminodiphenyl ether were added, the type of alcohol compound having an acryl or methacryl group, the number of diaminosiloxane bonds and mol% in Example 1 were used. Was changed, and Examples 2 to 6 and Comparative Examples 1 to 4 were performed. The results are shown in Table 1.

[0044]

[Table 1]

In Example 2, when glycerol dimethacrylate was used instead of 2-hydroxyethyl methacrylate in Example 1, the sensitivity was improved to 680 mJ / cm ² .
The elastic modulus was as low as 200 kg / mm ^2, and the adhesion was good.

In Example 3, when the 2-hydroxyethyl methacrylate of Example 1 was changed to pentaerythritol triacrylate, the sensitivity was improved to 350 mJ / cm ² . The elastic modulus is as low as 210 kg / mm ^2, and the adhesion is good,
The number of peeling was 0.

In Example 4, when the mol% of the diaminosiloxane of Example 1 was increased from 10 to 30, the elastic modulus showed a very low value of 80 kg / mm ² . Adhesion was also good, and the number of peeling was 0.

In Example 5, when the bonding number n of the diaminosiloxane of Example 1 was changed from 5 to 1, a polyamide having a high number average molecular weight of 23,000 and a weight average molecular weight of 59000 was obtained. The sensitivity was 800 mJ / cm ² , the adhesion was good, and the number of peeling was 0.

In Example 6, when the bonding number n of diaminosiloxane was changed to 9, the elastic modulus was 170 kg / mm ^2, which was a low value. Adhesion was also good, and the number of peeling was 0.

In Comparative Example 1, when DCC and diaminodiphenyl ether were dividedly added in Example 1 and added in one time without division, the number average molecular weight of the obtained polyamide was 11,000, and the weight average molecular weight was 11,000. Molecular weight is 35,000
Became low. The reaction rate of diaminosiloxane is'H-MN
When calculated by R, it was as low as 50.2%, and the number of peeled off was 78 in the adhesion evaluation, and there was a problem in normal use.

In Comparative Example 2, glycerol dimethacrylate was used as the alcohol compound having an acryl or methacryl group, and DCC and diaminodiphenyl ether were further added at once without division. The number average molecular weight of the obtained polyamide was 5000. , The weight average molecular weight is 1200
It became as low as 0. In the evaluation of adhesion, the number of peeling was 100, which was a problem for normal use.

In Comparative Example 3, 2-hydroxyethyl methacrylate of Example 1 was changed to pentaerythritol triacrylate, and DCC and diaminodiphenyl ether were added at once without splitting. When the polymer obtained by GPC was analyzed, it showed a trimodal molecular weight distribution.
It was found that the increase in the molecular weight did not proceed well. When a sensitizer and an inhibitor were added to this polymer in the same manner as in Example 1 to prepare a composition, gelation occurred on the second day, and it was found that the composition had low practicability.

In Comparative Example 4, when the mol% of diaminosiloxane was lowered to 0.1 mol%, the film was peeled off in the form of a film in the evaluation of adhesiveness, and it was found that the practicability was low.

[0054]

Industrial Applicability According to the present invention, it is possible to obtain a high molecular weight polyamide having an ester bond of an acrylic or methacrylic group, which cannot be obtained by a conventional method. Further, the photosensitive resin composition obtained from this photosensitive resin has high sensitivity, and the cured film obtained from this composition has very excellent adhesion and low elastic modulus.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location // C08F 299/02 MRU 7442-4J 299/08 MRY 7442-4J G03F 7/075 511 H01L 21 / 027 (72) Inventor Naoshi Takeda 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Sumitomo Bakelite Co., Ltd.

Claims (1)

[Claims] 1. 100 mol% of a dicarboxylic acid component obtained by previously reacting a tetracarboxylic dianhydride with an alcohol compound having an acrylic group or a methacrylic group represented by the formula (1) and a diamino represented by the formula (2). Siloxane 0.5-50
When reacting a diamine component consisting of 99.5 to 50 mol% of aromatic diamine with 9% to 50 mol% of aromatic diamine using carbodiimides as a condensing agent, a predetermined amount of the required diamine component and carbodiimides are added to the total acid component. A method for producing a photosensitive resin, characterized in that the addition reaction is carried out, and the addition of diaminosiloxane is completed before the final stage of the addition. [Chemical 1] [Chemical 2]